Treatment of materials made of or containing cellulose derivatives



ll atenlzerl. lllleyy GEORGE HOLLAND EJ 11115, 0F SPONDON, NEAR DERBY, ENGLAND, ASSIGNOR TO CELA- NESE COBEORATION OF AMERICA, A CORPORATION OF DELAWARE TREATMENT OF MATERIALS MADE OF OR CONTAINING CELLULOSE DERIVATIVES No Drawing. Application filed March 25, 1827, Serial No. 178,505, and in Great Britain October 30, 1926.

This invention relates to the lllflldtlllllllg of yarns or threads, or woven. lcuitteil or other textile fabrics, hints or other Pl'Olllltltmade of or containing cellulose acetate or other organic acid esters of cellulose. for ex ample, cellulose tormate, propionate or hut rate, or made of or cont aining cellu lose ethers. such as methyl, ethyl or henzyl eellulose or the corresponding condensation products of m cellulose and glycols or other I)()l '\'ll:l,'(ll'l(' tllt'O- hols. all of which are hereinafter referred to as organic substitution derivatives of cell ulose.

ltn dyeing cellulose acetate materials by tiret morrlanting and then dyeing. it has pie vionsly been proposed to apply the metallic mordants in the form of thioeyanatee.

lt has now been found that the ahsorption of the lliOl'tlEHllJ by the cellulose acetate muteon rials is largely influenced by the eoneeullrm tion of the thiocyanate grouping present in the morclanting liquor quite apart from the concentration of the metallic ltltllt'lt, itself. Thus, h v increasing the C(JIICOlllZlZll'lllll ot the thioeyanate railicle compared with that of the n'ietallic racliele. it has been touml posl to effect a higher degree of aliisorptimi the in e-llic racliele than with a morrlantliquor containing the same eoneentralion an of metallic eacliele together with the ehemically equivalent ccnicentration oi thim-yaimto ratllcle or alternatively to eltecl: an equivalent degree of inortlanting to that ohtai iahle with molecular. proportions or metal null thiolanatc whilst'using consitlerahly lmver eon" cen tion of th metallic ratliclt-n ting process, i. e. using higher r1 i) til Thisniolm. than molecule. concentrations (it thioeyanatc is tnrtheapplicable to the mortlantiiug of materials made oi or containing any other of the aforesaid organic substitution derivatives of cellulose.

l'lccortlinggl wthe present invention con): prises nunrtlanting materals matle of or eontanning cellulose acetate or other or the aforesaid organic suliistitution lltiflVtlLiVEf-l of cellulose with solutions or pastes containing the thioeyanate rat hole in a concentration in err-- ees-e oi that which is chemically euui mlent to the IDOHltllll metal railiele present in the solution or paste.

The increase in the thioevauate concentration may for example he ell'eetell by tltltlltion to the thioeyanate of the morrlant metal or metals of a thiocyauate of a base not show ing mordant properties, for instance ammo nium thioe alnite. or sodium or potassium thiocyanate. or alternatively such a thioe t anate may he added to a salt of a mortlant metal in excess of the chemically equivalent q uantit' v.

The improved ahsorption of the mortlants euahles the operation of lmirilanting to he carried out more expeditiously, or more eonreniently in bulk practice. and elleetive mor- (hinting); may for example he achirwerl hy continuous means. the material heingr merely passed through the lll01'tllllllllll' liquor. the .superlluoua liquor preterahl squeezed out. and the materials allowed to lie until the maximum amount of morrlanlin r has taken place lin atlelition to an 'intensilieution oil moo rlanting resulting" in :ulrantagres in ti1ne.,temperature. eom-entralion aurl manipulaliw factors, the methocl according to the preueut invention is also inlrautageoiu: in that it; clirninishes the risk of ohtaininn u eurlin-e tilposit oil the mormlant with eons-ieuuent llflltleney ot the dyeing or coloring to ruh oil or to he lee; lustrous.

in carrying out; the invention so aeto mow rlaut the whole o'l. a tahrie the taluie only he. hroiug'ht into a liquor containing; a 'lhionmate of a metallic rarlicle lllr ll'tll tor or capable o'l" yielding: results; in niorllantin such for example as iron. aluminum. ltl'l inium anti the like (or mixtures ot' ouch) ulul a thioeyanatc ol a non-moralerating uu tal liaise, enel'l as unnnonium. smlium or ])(llTFlFL-- fillllll thiocyanate.

The amount oi. lillll'tltlllli requiret ally be governed hy the tlepth oi mately elesirell, and. the commnti perature anrl time of ltreatn'ient may ho rietl ae V liugi ly.

'lhe lollo'wlng ominplen at given. in" era oi illustration. it hemp; mule ii that they are in no Way liniitatire.

Example 1 To mordant 100 lbs. of cellulose acetate Woven fabric with iron. The cellulose acetate material is treated in any suitable manner for about 1 hour at about 75 C. in a. bath (approximately 30: 1 on the goods) made up with liquor so as to contain 54 grams of ferric chloride (0.33 gram molecules) and 152 grams of ammonium thimryanate (2 grain molecules) per litre. The material is then removed and washed off first in cold and then in warm water until there is a change in shade from a deep red to a golden yellow color. The hydrolysis of the tl1l()C tl1lfltO of iron may conveniently be completed by treatment in a separate bath containing 5 grams of sodium carbonate per litre at 3035 C. for

. 5-10 minutes. After rinsing, the goods are 20 ready for the dyeing operation.

Example 2 A similar mordanting result to that obtained according to the process of Example 1 may be achieved alternatively in a manner especially suitable to bulk production. The fabric is passed continuously by means of any suitable machine through a liquor containing ferric chloride and ammonium. thiocyanate in similar concentrations to those used in the foregoing example. the fabric. after passage through the liquor. being squeezed between rollers adjusted so that the goods retain about their own weight of liq- .101. The temperature may conveniently be adjusted to about 50 C. After squeezing the goods are allowed to lie for about 12 hours, conveniently overnight. They are then sub jected to Washing and/or sodium carbonate treatment for hydrolysis of the thiocyanate of iron as described in Example 1. The goods may then be dyed as desired. for example a full black shade may be produced by treatment at about 75 C. in a bath containing 10% haen'iatine' crystals on the weight of the goods.

Example 3 To mordant with chrome 100 lbs. of cellulose acetate yarn in the form of hanks. The goods are treated for 1 hour atabout 75 C. in a bath having a ratio to the goods of approximately 30:1 and containing 53 grams of chromium chloride (0.33 gram molecules) and 114 grams of ammonium thiocyanate (1.5 gram molecules) per litre. After this treatment the cellulose acetate material is washed 0d at 30 C. for 510 minutes in a solution of soda ash (5 TW.). Subsequently the material is rinsed in soft water. The yarn may then be dyed as desired, for instance if dyed with 2"}, alizarine on the weight of the goods at 75 C. a deep maroon color is obtained.

Example .1}

To mordant with aluminium 100 lbs. of cellulose acetate knitted fabric. The fabric is treated for 1 hour at C. in bath of approximately 30:1 ratio to the goods and containing 107 grams of aluminium chloride (0.8 gram molecules) and 274 grams of ammonium thiocyanate (3.6 gram molecules) per litre. The material is then washed off at 30 C. for 540 minutes in a solution of soda ash (5 Tw.). The material may subsequently be rinsed in soft 'ater and dyed as desired, for instance if dyed with 2% alizarine on the weight of the goods at 75 C. a bright red is produced.

The process is applicable. in addition to the mordanting and dyeing of the whole of a fabric or other material. to the local application of mordants and mordant dyestuffs for example by printing or stencilling by methods known in the art.

The process of the present invention may be applied to goods composed wholly of cellulose acetate or other of the aforesaid organic substitution derivatives of cellulose, or to mixed goods containing for example, in addition to one or more of the aforesaid organic substitution derivatives of cellulose, wool, cotton, natural silk, artificial silk of the cellulose type etc.

What I claim and desire to secure by Letters Patent is 2- 1. A process of mordanting materials comprising organic substitution derivatives of cellulose. which comprises applying the metallic mordants thereto in the form of thiocyanates, the concentration of thiocyanate radicle present being in excess of that chemically equivalent to the mordant metal radicle.

A process of mordanting materials comprising cellulose acetate which comprises treating" the materials in a solution of the thiocyanate of the mordant metal containing the thiocyanate radicle in a concentration in excess of that chemically equivalent to the mordantmetal radicle.

In testimony whereof I have hereunto subscribed my name.

' GEORGE HOLLAND ELLIS. 

